CN113466387A - Py-HPLC detection system and detection method - Google Patents
Py-HPLC detection system and detection method Download PDFInfo
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Abstract
The application belongs to the technical field of RoHS detection, and specifically discloses a Py-HPLC detection system, including the dress appearance system: the sample loading device is used for loading samples; a thermal cracking system: used for thermally cracking a sample to be detected; an absorption system: used for absorbing the products of the sample to be tested after thermal cracking; high performance liquid chromatography system: for detecting the product; the sample loading system, the thermal cracking system, the absorption system and the high performance liquid chromatography system are sequentially connected through pipelines. The application has at least one of the following beneficial effects: the application provides a Py-HPLC detecting system, it carries out high performance liquid detection through carrying out the sample schizolysis back to await measuring for need not to carry out the pretreatment to the sample that awaits measuring, shorten sample test cycle greatly, can make full use of high performance liquid chromatography detect's advantage moreover, for example need not high temperature, the antipollution ability is strong, instrument cost low grade, makes it have extensive using value in the RoHS management and control.
Description
Technical Field
The application belongs to the technical field of harmful substance (RoHS) detection in electric and electronic products, and particularly relates to a Py-HPLC detection system and a detection method.
Background
With The implementation of environmental regulations for Electronic and Electrical products around The world, for example, "The Restriction of The use of a real Hazardous substructures in Electronic and Electronic Equipment" (RoHS directive), and "Hazardous substance Restriction and use management method for Electronic and Electrical products" in China, etc. The use of harmful substances is limited by the electric and electronic products, especially the organic harmful substances such as phthalic acid esters (Phthalates), polybrominated biphenyls (PBBs), polybrominated diphenyl ethers (PBDEs) and the like, and the sample detection is still one of the product conformity evaluation technologies. Due to the fast update of electric and electronic products (especially consumer electronic products), the RoHS detection period of the products cannot be too long, otherwise the release of new products is influenced.
In the technical field of RoHS detection, there are two development directions: the first is the traditional chemical confirmation analysis detection technology, and the other is the rapid screening detection technology. The traditional chemical confirmation analysis detection technology has accurate test result, but the test process is complicated and the time consumption is long. For example, for testing the content of organic harmful substances in a sample, chemical validation analysis and detection generally comprises sampling, sample pretreatment (soxhlet extraction), extract purification, machine test and test result calculation, wherein the detection process takes longer time, wherein the sampling lasts for 10 minutes, the pretreatment process lasts for at least 2 hours, the purification process lasts for 20 minutes, the machine test lasts for at least 30 minutes, and the test result can be obtained only after one sample is tested for at least 3 hours. However, generally, a complete machine of an electric appliance and an electronic product has 500 detection unit samples, so that the complete machine needs at least 1 month of time for all the tests by using the chemical validation analysis detection technology RoHS (considering that 4 detection unit samples can be pretreated simultaneously in parallel). If the sample is not good in extraction efficiency, the pretreatment process time is longer, and therefore, the whole test time is also longer. Meanwhile, the pretreatment process in the chemical validation analysis testing process has the risk of sample cross contamination.
The rapid screening test technology is one of the other development directions of the future RoHS detection technology, according to the regulations in the national standard GB/T39560.1-2020 of determination of certain substances in electronic and electrical products of the RoHS detection industry, the screening test is an analysis method for determining whether certain substances are contained in a representative part or a component of a product, the method compares the presence or absence of harmful substances with corresponding limit values set by further detection to determine a test result, and the rapid screening test technology is particularly suitable for the RoHS detection field.
X-ray fluorescence spectroscopy (XRF) screening test techniques and apparatus have been developed in the RoHS detection field, and are incorporated into the relevant international/national standard for RoHS detection. However, due to technical implementation and operation reasons, XRF can only screen and test inorganic element harmful substances (such as Pb, Hg and the like) and cannot screen and test organic harmful substances (such as phthalates, PBBs, PBDEs and the like), so that the XRF screening test cannot cover all RoHS harmful substances, and the application range of the XRF screening test in RoHS testing is limited.
Disclosure of Invention
Based on the detection method, the thermal cracking-high performance liquid chromatography combined (Py-HPLC) detection system is provided, the system does not need to carry out pretreatment on a sample, the detection flow is simplified, and the system can detect organic harmful substances in all RoHS detection fields.
The application is realized by the following scheme:
the application provides a Py-HPLC detecting system, it includes: a sample loading system: the sample loading device is used for loading samples; a thermal cracking system: used for thermally cracking a sample to be detected; an absorption system: used for absorbing the products of the sample to be tested after thermal cracking; high performance liquid chromatography system: for detecting the product; the sample loading system, the thermal cracking system, the absorption system and the high performance liquid chromatography system are sequentially connected through pipelines.
In the application, a thermal cracking system is adopted to thermally crack a sample to be detected, so that organic harmful substances contained in the sample to be detected are released, the cracked product is detected by a high performance liquid chromatography system (provided with a detector), the sample can be directly injected without pretreatment and purification, and the test time of the sample is greatly shortened, wherein the detector can be an ultraviolet detector (UV) or a fluorescence detector (FLD) or other types of detectors.
In one embodiment of the present application, the sample to be tested after pyrolysis by the thermal cracking system is introduced into the absorption system by a carrier gas.
In one embodiment of the present application, the carrier gas is an inert gas, for example, the carrier gas is nitrogen, argon, helium, or the like.
In the present application, the carrier gas pressure fluctuation is less than: 0.1 percent and the fluctuation of the carrier gas flow is less than or equal to 1 percent.
In one embodiment of the present application, the absorbent system comprises an absorbent.
In the application, the carrier gas is introduced into the absorption system, and the cracked product is absorbed by the absorbent, so that the solubility of the cracked product is increased, and the concentration of the cracked product is improved.
In one embodiment of the present application, the absorbent is added cyclically. In the application, the absorbent is added in a circulating manner, and the absorbent reduced by entering the high performance liquid chromatography system is supplemented in time, so that the absorbent in the absorption system is kept continuously supplied.
In one embodiment of the present application, the absorbent can be selected according to the properties of the substance to be tested (e.g., the solubility of the substance to be tested, etc.) and the characteristics of the high performance liquid phase in the prior art. Preferably, the absorbent is an organic solvent, such as toluene, acetonitrile, and the like.
In one embodiment of the present application, the absorption system comprises a sample pump, and the cracked product is dissolved in an absorbent and enters the high performance liquid chromatography system through the sample pump.
In a specific embodiment of this application, the absorption system still includes the filter valve, the product after the schizolysis is gone into after filtering the sampling pump gets rid of the solid impurity who gets into the sample in the high performance liquid chromatography system, prevents that solid impurity from polluting the high performance liquid chromatography system.
In one embodiment of the present application, the thermal cracking system has a temperature programming function, wherein the temperature range is from room temperature to 600 ℃; the temperature rise rate control range is as follows: 1 to 30 ℃/min; the temperature control precision is as follows: 1 ℃ C. In the detection process, a temperature rise program of the thermal cracking system can be set according to the type of the target substance to be detected and the type of the base material.
In a specific embodiment of this application, dress appearance system is automatic dress appearance system, automatic dress appearance system includes sample cup, sample cup elevating platform and sample cup ejection of compact mouth, the sample cup is used for loading the sample that awaits measuring, loads the sample cup that awaits measuring the sample passes through the sample cup elevating platform transports extremely thermal cracking system, and the sample cup after the schizolysis is accomplished pops out through sample cup ejection of compact mouth.
In another aspect, the present application provides a Py-HPLC detection method, comprising the following steps:
s1: putting the sample into a sample loading system;
s2: a thermal cracking system to crack the sample;
s3: the absorption system absorbs the cracked product
S4: detecting the product by a high performance liquid chromatography system.
The Py-HPLC detection system provided by the application has at least one of the following beneficial effects:
the application provides a Py-HPLC detecting system, it detects through carrying out high performance liquid chromatography behind the sample schizolysis that will await measuring for need not to carry out the preliminary treatment to the sample that awaits measuring, shorten sample test cycle greatly, can make full use of high performance liquid chromatography detect's advantage moreover, for example need not high temperature, the antipollution ability is strong, instrument cost low grade, makes it have extensive using value in the management and control of RoHS.
Drawings
FIG. 1 is a schematic diagram of a Py-HPLC detection system provided in the examples of the present application.
Wherein, 100-automatic sample loading system; 101-a sample cup; 102-sample cup ejection port; 103-sample cup lifting stage; 200-a thermal cracking system; 300-an absorption system; 301-an absorbent; 400-high performance liquid chromatography system; 401-sample pump; 402-a filter valve.
FIG. 2 is an HPLC chromatogram for detecting standard substances containing BBP, DIBP, DBP and BDE-209 provided in the examples of the present application.
Wherein, 1-BBP; 2-DIBP; 3-DBP; 4-BDE 209.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
EXAMPLE 1 Py-HPLC detection System
As shown in fig. 1, the Py-HPLC detection system provided in this embodiment specifically includes an automatic sample loading system 100, a thermal cracking system 200, an absorption system 300, and a high performance liquid chromatography system 400, wherein the automatic sample loading system 100, the thermal cracking system 200, the absorption system 300, and the high performance liquid chromatography system 400 are sequentially connected through a pipeline. The autosampler system 100 includes a sample cup 101, a sample cup lift 103, and a sample cup ejection port 102. The sample cup 101 containing the sample to be measured is transported to the thermal cracking system 200 by the sample cup elevating table 103, and the thermally cracked sample cup 101 is ejected through the sample cup ejection port 102 for loading the next sample.
The thermal cracking system 200 cracks a sample to be tested. The cracked product of the sample to be tested is introduced into the absorption system 300 by the carrier gas. The absorbent 301 in the absorption system absorbs the cracked product, and after being filtered by the filter valve 402, the product is pumped into the HPLC for detection by the sample pump 401.
The thermal cracking system 200 has a temperature programming function, wherein the temperature rise range is from room temperature to 600 ℃, and the temperature rise rate control range is from 1 ℃/min to 30 ℃/min; temperature control accuracy: 1 ℃ C.
The pressure fluctuation of the carrier gas is less than or equal to (3) 0.1%, and the carrier gas flow fluctuation is less than or equal to 1%. The absorbent in the absorption system can be added circularly, and the absorbent can be supplemented in time, so that the absorbent is ensured to be in a certain concentration range.
The hplc in the hplc system 400 may be configured with an ultraviolet detector (UV) or a fluorescence detector (FLD) or other type of detector according to the kind of the test target.
Application example 1
The content of decabromodiphenyl ether (BDE-209), Butyl Benzyl Phthalate (BBP) and diisobutyl phthalate (DIBP) in a polyvinyl chloride (PVC) substrate and the content of BDE-209 and dibutyl phthalate (DBP) in a PE sample were measured by using the Py-HPLC detection system in example 1, and the specific procedures are as follows:
(1) accurately weighing 0.50mg of sample PVC base material;
(2) placing a sample into a sample cup 101, and placing the sample cup 101 into the automated sample loading system 100;
(3) the absorbent 301 is toluene.
(4) Setting the temperature-raising program of the thermal cracking system 200: 200 ℃→ (20 ℃/min) → 300 → (5 ℃/min) → 340 ℃ (hold 1 min), the thermal cracking temperature increasing program operating time being 15 min;
(5) HPLC test system parameters and settings were as follows, run time 30 min:
1) column C18: 250 mm × 4.6 mm × 5.0 μm;
2) mobile phase: mobile phase A: acetonitrile, mobile phase B: water, mobile phase gradient program: see table 1;
3) column temperature: (35 +/-0.2) DEG C;
4) detection wavelength of the ultraviolet detector: 226 nm
TABLE 1 HPLC mobile phase gradient program
(6) Starting the test;
(7) and calculating a test result. The detection results of the traditional Soxhlet extraction pretreatment and GC-MS method in GB/T39560.6-2020 and GB/T39560.8-2021 are used as a reference, and the experimental results are shown in FIG. 2 and Table 2.
TABLE 2 comparison of results
As can be seen from fig. 2, the Py-HPLC detection system provided in example 1 can also be used to simultaneously detect four substances, BDE-209, BBP, DBP and DIBP, and as can be seen from table 2, the recovery rates of the four substances detected by the Py-HPLC detection system provided in example 1 are all between 80% and 110%, and the relative deviations compared with the test results of the conventional "soxhlet extraction pretreatment + GC-MS" method are all within 10%, which meets the technical requirements of RoHS screening test. Meanwhile, when the Py-HPLC detection system provided in example 1 is used for detection, in addition to the time for loading the sample into the sample cup (about 3 min), the time required for testing one detection unit sample does not exceed 60min, which is much shorter than the testing period (3 hours/one sample) for testing BDE-209 according to the method of Soxhlet pre-extraction + GC-MS in the standard GB/T39560.6-2020 and the testing period (nearly 6 hours/one sample) for testing DBP and DEHP according to the method of Soxhlet pre-extraction + GC-MS in the standard GB/T39560.8-2021. Therefore, the method disclosed by the invention not only can meet the RoHS detection requirement in accuracy, but also can greatly shorten the sample test period and improve the detection efficiency.
In conclusion, the Py-HPLC detection system provided by the application greatly shortens the detection time of organic harmful substances in RoHS detection, and the whole process of testing one detection unit by using the technology (equipment) is within 1 hour; the Py-HPLC detection system can directly sample, and does not need to carry out pretreatment (Soxhlet extraction) and purification treatment on the sample, so that the risks of cross contamination and the like of the sample in the treatment process are avoided; because the thermal cracking sample injection equipment and the high performance liquid chromatograph are made in a home-made mode, the Py-HPLC detection system provided by the application expands the application field of home-made analysis and test instruments and equipment and promotes the technical development of the home-made analysis and test instruments and equipment; the detection system combines the screening test of organic harmful substances in the RoHS detection field of electric and electronic products with the XRF test technology which can only be used for the screening test of inorganic element harmful substances, can cover the screening test of all harmful substances (organic and inorganic elements) in the RoHS detection field, and promotes the development of the RoHS screening test technology.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A Py-HPLC detection system, comprising:
a sample loading system: the sample loading device is used for loading samples;
a thermal cracking system: used for thermally cracking a sample to be detected;
an absorption system: used for absorbing the products of the sample to be tested after thermal cracking;
high performance liquid chromatography system: for detecting the product;
the sample loading system, the thermal cracking system, the absorption system and the high performance liquid chromatography system are sequentially connected through pipelines.
2. The detection system according to claim 1, wherein the sample to be detected after pyrolysis by the thermal cracking system is introduced into the absorption system by a carrier gas.
3. The detection system of claim 1, wherein the absorption system comprises an absorbent.
4. A detection system according to claim 3, wherein the absorbent is an organic solvent.
5. The detection system of claim 1, wherein the absorbent is added cyclically.
6. The detection system of claim 1, wherein the absorption system comprises a sample pump, and the cracked product enters the high performance liquid chromatography system through the sample pump.
7. The detection system of claim 6, wherein the absorption system further comprises a filter valve, and the cracked product is filtered and then enters the sample pump.
8. The detection system of claim 1, wherein the thermal cracking system is capable of programmed temperature rise, wherein the temperature rise is in a range from room temperature to 600 ℃; the temperature rise rate control range is as follows: 1 to 30 ℃/min; the temperature control precision is as follows: 1 ℃ C.
9. The testing system of claim 1, wherein the sample loading system is an automatic sample loading system, the automatic sample loading system comprises a sample cup, a sample cup lifting platform and a sample cup ejection port, the sample cup is used for loading a sample to be tested, the sample cup loaded with the sample to be tested is transported to the thermal cracking system through the sample cup lifting platform, and the sample cup after completion of the cracking is ejected through the sample cup ejection port.
10. A Py-HPLC detection method is characterized by comprising the following steps:
s1: putting the sample into a sample loading system;
s2: a thermal cracking system to crack the sample;
s3: the absorption system absorbs the cracked product
S4: detecting the product by a high performance liquid chromatography system.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115469030A (en) * | 2022-09-14 | 2022-12-13 | 中国电子技术标准化研究院 | Quick screening and testing method for polybrominated diphenyl ether in polymer material of electronic and electric products |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2435751A1 (en) * | 1978-09-08 | 1980-04-04 | Electricite De France | Automatic transporter for moving samples to test enclosure - incorporate horizontal and vertical conveyors, esp. applicable in measuring radioactivity of samples from nuclear power stations |
| FR2517832A1 (en) * | 1981-12-09 | 1983-06-10 | Electricite De France | Measuring the weak gamma radioactivity of liq. samples - where sample flasks are conveyed by turntable to measuring pit in which hoist lowers flask to radiation detector |
| US5866072A (en) * | 1996-02-26 | 1999-02-02 | Cds Analytical, Inc. | Analytical pyrolysis autosampler |
| CN102507807A (en) * | 2011-10-13 | 2012-06-20 | 云南烟草科学研究院 | Trapping analysis method and trapping device for phenol in pyrolysis products of exogenous additives |
| JP2014182037A (en) * | 2013-03-19 | 2014-09-29 | Toyota Central R&D Labs Inc | Volatile cracked component collection and recovery device, liquid chromatograph and volatile cracked component analysis method |
-
2021
- 2021-05-26 CN CN202110580483.7A patent/CN113466387A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2435751A1 (en) * | 1978-09-08 | 1980-04-04 | Electricite De France | Automatic transporter for moving samples to test enclosure - incorporate horizontal and vertical conveyors, esp. applicable in measuring radioactivity of samples from nuclear power stations |
| FR2517832A1 (en) * | 1981-12-09 | 1983-06-10 | Electricite De France | Measuring the weak gamma radioactivity of liq. samples - where sample flasks are conveyed by turntable to measuring pit in which hoist lowers flask to radiation detector |
| US5866072A (en) * | 1996-02-26 | 1999-02-02 | Cds Analytical, Inc. | Analytical pyrolysis autosampler |
| CN102507807A (en) * | 2011-10-13 | 2012-06-20 | 云南烟草科学研究院 | Trapping analysis method and trapping device for phenol in pyrolysis products of exogenous additives |
| JP2014182037A (en) * | 2013-03-19 | 2014-09-29 | Toyota Central R&D Labs Inc | Volatile cracked component collection and recovery device, liquid chromatograph and volatile cracked component analysis method |
Non-Patent Citations (8)
| Title |
|---|
| JAE WOO KIM 等: "Comparative study of thermal desorption and solvent extraction-gas chromatography–mass spectrometric analysis for the quantification of phthalates in polymers", JOURNAL OF CHROMATOGRAPHY A * |
| 余淑媛 等: "热解分离-气相色谱-质谱联用法测定聚苯乙烯电器外壳中20种多溴联苯和多溴联苯醚", 理化检验(化学分册) * |
| 张艳芳 等: "高效液相色谱法测定烟用白乳胶中邻苯二甲酸酯类化合物", 《理化检验(化学分册)》 * |
| 赵银平 等: "SPE和 HPLC对微生物降解体系中十溴联苯醚含量的测定", 湖北农业科学 * |
| 赵银平 等: "SPE和HPLC对微生物降解体系中十溴联苯醚含量的测定", 《湖北农业科学》 * |
| 陈建华 等: "溶剂捕集-高效液相色谱法测定烟用添加剂热裂解产物中的苯酚", 《云南大学学报(自然科学版)》 * |
| 陈海燕 等: "高效液相色谱法测定生活用纸杯中16种邻苯二甲酯含量的研究", 广东化工 * |
| 高坚 等: "高效液相色谱法测定电子电气产品中四种增塑剂", 信息技术与标准化 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115469030A (en) * | 2022-09-14 | 2022-12-13 | 中国电子技术标准化研究院 | Quick screening and testing method for polybrominated diphenyl ether in polymer material of electronic and electric products |
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